JP2012083651A - Colored resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter being excellent in brightness, contrast and the like, having vivid and high quality color characteristics, and also being more excellent in resistance and the like than those of conventional filters and having higher reliability.SOLUTION: A colored resin composition for manufacturing a color filter of the present invention is easily obtained by using a certain coloring agent compound, and in addition by mixing a binder resin, a solvent, a hardener and the like. The manufactured color filter is excellent in color characteristics such as high contrast and has high quality, and further it is excellent in heat resistance and the like and has high reliability.

Description

  The present invention relates to a colored resin composition for forming pixels such as blue, red, and green, a color filter formed using the same, a liquid crystal display device formed using the color filter, and an image sensor (CCD, CMOS). ), And an electronic display device such as an organic EL display.

  For colorization of liquid crystal display elements such as liquid crystal displays (LCD) typified by notebook computers, liquid crystal televisions, mobile phones, etc., and image sensors (CCD, CMOS) used as input devices for digital cameras, color copiers, etc. A color filter is required. As a method for producing a color filter used in these liquid crystal display devices and solid-state image sensors, there are a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, and the like. In recent years, the pigment dispersion method has become the mainstream. As a patterning method, a photolithography method is typical, and a color filter is formed using a mixture of a photosensitive resin composition and a pigment dispersion. Recently, a method of forming a color filter by applying a colored ink directly on a substrate without using a mask by an ink jet printer is also performed.

  Improvements in color purity, saturation, brightness, and contrast, which are characteristics required for color filters, are particularly important. By improving the brightness, the amount of light of the backlight can be suppressed and the power consumption can be reduced, so this is an environmentally necessary technology. In order to improve the color purity of the color filter, it is necessary to increase the content of the color pigment or to select a pigment having a better spectral waveform. On the other hand, since it is necessary to increase the transmittance in order to improve the brightness, the pigment concentration must be reduced or the film thickness must be reduced. In order to make these contradictory properties compatible, a method of making fine particles of pigment has been studied, but there is a limit to the resistance to fine particles and dispersion stability, and even if the brightness is improved, it is not possible to achieve both resistance and resistance. is the current situation.

  In order to solve these problems, a color filter using a dye is being studied as another approach. If a dye is used, there is a merit that the contrast can be improved because the light purity can be suppressed because the color purity and lightness cannot be achieved by a pigment, and the particles are not particles. However, for display bodies that require long-term reliability such as televisions, light resistance and heat resistance are necessary, but in particular, blue dyes are much less resistant than pigments. For example, Patent Documents 1 and 2 report on a color filter using a triphenylmethane compound, but the triphenylmethane compound is extremely inferior in light resistance and heat resistance and is not at a practical level. Patent Document 3 describes that xanthene compounds are excellent in lightness, but does not describe resistance. A colored resin composition containing a colorant compound having excellent durability in a color filter that requires high reliability is required, but it is not practically used at present. Accordingly, there is a need for a high-quality color filter that is excellent in brightness, contrast, and durability as a next-generation product.

JP-A-8-94826 Japanese Patent Laid-Open No. 2002-14222 JP-A-60-249102 JP 63-172772 A

  An object of the present invention is to provide a color filter having excellent heat resistance and high contrast.

  As a result of diligent research to solve the above problems, the present inventor has found that the above problems can be solved by using a colored resin composition containing a specific color material compound in order to produce a pixel of a color filter. The present invention has been completed.

（式（１）において、Ｒ_１a〜Ｒ_６aは、それぞれ独立に水素原子、ハロゲン原子、Ｃ１−Ｃ１２のアルキル基、Ｃ１−Ｃ１２のアルコキシ基、ニトロ基、カルボキシル基、アルコキシカルボニル基を表す。Ｒ_７a〜Ｒ_１０aはそれぞれ独立に水素原子、Ｃ１−Ｃ１２のアルキル基、アリール基を表す。Ｒ_１１a〜Ｒ_１５aはそれぞれ独立に水素原子、Ｃ１−Ｃ１２のアルキル基、Ｃ１−Ｃ１２のアルコキシ基、ハロゲン原子、ニトロ基、フェノキシ基、カルボキシル基、アルコキシカルボニル基、スルホ基、スルファモイル基の１種または２種以上を有していてもよい。アニオン部はＣ１−Ｃ１０の高次ハロゲン化アルキルスルホネートであり、少なくとも一つのハロゲン原子Ｘを有する(ｎ＝１〜１０、１≦ｍ≦２ｎ＋１、Ｘはハロゲン原子のいずれでもよい）、
（２）トリフルオロメタンスルホネートをアニオン部とする式（１）で表される色材化合物を含む（１）に記載の着色樹脂組成物、
（３）金属フタロシアニン顔料を含む（１）又は（２）に記載の着色樹脂組成物、
（４）下記式（２）で表される色材化合物を含む（１）乃至（３）のいずれか一つに記載の着色樹脂組成物

（式（２）において、Ｒ_１ｂ〜Ｒ_６ｂはそれぞれ独立に水素原子、Ｃ１−Ｃ３０のアルキル基、フェニル基またはベンジル基を表すが、少なくとも１つはＣ１−Ｃ３０のアルキル基である。Ｒ_７ｂ〜Ｒ_２０ｂは、それぞれ独立に水素原子、ハロゲン原子、Ｃ１−Ｃ６のアルキル基を表す。Ｚ⁻はＣ１−Ｃ１０の高次ハロゲン化アルキル基を有するアルキルスルホニルイミドアニオン、アルキルスルホニルメチドアニオン、又はアルキルスルホネートを表す）、
（５）式（２）のアニオン部Ｚ⁻がビストリフルオロメタンスルホニルイミドアニオン、トリストリフルオロメタンスルホニルメチドアニオン又はトリフルオロメタンスルホネートである式（２）で表される色材化合物を含む（１）乃至（４）のいずれか一つに記載の着色樹脂組成物、
（６）（１）乃至（４）のいずれか一つに記載の着色樹脂組成物を用い、パターニングされてなるカラーフィルター用着色硬化膜、
（７）（６）に記載のカラーフィルター用着色硬化膜からなるカラーフィルター、
（８）（７）に記載のカラーフィルターを装着してなる液晶表示装置および有機ＥＬディスプレイ、
（９）（８）に記載のカラーフィルターを装着してなる固体撮像素子、
に関する。 That is, the present invention
(1) A colored resin composition for a color filter containing a colorant compound represented by the following formula (1), a binder resin, a solvent, and a curing agent.

(In Formula (1), R < _1a > -R < _6a > respectively independently represents a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a nitro group, a carboxyl group, and an alkoxycarbonyl group. _7a to R _10a each independently represent a hydrogen atom, an alkyl group of C1-C12, an aryl group _{.R 11a} to R _15a each independently represent a hydrogen atom, C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen It may have one or more of atoms, nitro group, phenoxy group, carboxyl group, alkoxycarbonyl group, sulfo group, sulfamoyl group, and the anion part is a C1-C10 higher order halogenated alkyl sulfonate. , Having at least one halogen atom X (n = 1 to 10, 1 ≦ m ≦ 2n + 1, X is a halogen atom Any of these)
(2) The colored resin composition according to (1), including a colorant compound represented by formula (1) having trifluoromethanesulfonate as an anion moiety,
(3) The colored resin composition according to (1) or (2), which contains a metal phthalocyanine pigment,
(4) The colored resin composition according to any one of (1) to (3), comprising a colorant compound represented by the following formula (2):

(In Formula (2), R _{1b to} R _6b each independently represents a hydrogen atom, a C1-C30 alkyl group, a phenyl group, or a benzyl group, but at least one is a C1-C30 alkyl group. R _7b to R _20b each independently represent a hydrogen atom, a halogen atom, .Z represents an alkyl group of C1-C6 ^- alkylsulfonyl imide anion having a higher halogenated alkyl group C1-C10, alkylsulfonyl methide anion, or Represents an alkyl sulfonate),
(5) The colorant compound represented by the formula (2), wherein the anion part Z ⁻ of the formula (2) is a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion, or a trifluoromethanesulfonate (1) to (1) (4) The colored resin composition according to any one of
(6) A colored cured film for a color filter, which is patterned using the colored resin composition according to any one of (1) to (4),
(7) A color filter comprising the colored cured film for a color filter according to (6),
(8) A liquid crystal display device and an organic EL display comprising the color filter according to (7).
(9) A solid-state imaging device comprising the color filter according to (8),
About.

  The colored resin composition of the present invention can provide a high-quality color filter having excellent heat resistance and high contrast by using a specific color material compound in the colored resin composition.

  The colored resin composition of the present invention contains a binder resin, a solvent, a curing agent, and a specific colorant compound, and if necessary, a colorant compound such as other pigment or dye, a surfactant, and photopolymerization initiation. Various additives such as an agent, a thermal polymerization initiator, a polymerization inhibitor, and an ultraviolet absorber can be contained, but are not limited to these, and can be used without particular limitation as components other than the specific color material compound. .

  The pixel manufacturing method using the colored resin composition of the present invention mainly includes a photolithography method and an inkjet method, and the former includes a photosensitive resin composition excellent in developability using a photo-opening polymerization initiator. The latter does not necessarily require a photopolymerization initiator, and a thermosetting resin composition is used.

The specific color material compound used in the present invention is represented by the formula (1), and R _{1a to} R _6a in the formula (1) are each independently a hydrogen atom, a halogen atom, a C1-C12 alkyl group, A C1-C12 alkoxy group, a nitro group, a carboxyl group, and an alkoxycarbonyl group are represented. R _{7a to} R _10a each independently represents a hydrogen atom, a C1-C12 alkyl group, or an aryl group. R _{11a to} R _15a are each independently a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen atom, a nitro group, a phenoxy group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, or a sulfamoyl group. Or you may have 2 or more types. The anion moiety represents trifluoromethyl sulfonate.

As a halogen atom in R _{< 1a} > -R < _15a > of Formula (1), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

Examples of the alkyl group in R _{1a to} R _15a in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and an iso group. Examples include C1-C12 alkyl groups such as -butyl group, n-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, and cyclohexyl group. These alkyl groups may have a substituent. Examples of the substituent include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a 2-sulfoethyl group, a carboxyethyl group, a cyanoethyl group, a methoxyethyl group, Examples thereof include an ethoxyethyl group, a butoxyethyl group, a trifluoromethyl group, a pentafluoroethyl group, a carbamoyl group, and a carboxyl group.

Examples of the alkoxy group in R _{1a to} R _15a of the formula (1) include an alkoxy group having a C1-C12 alkyl group in the same alkyl group as described above. An alkoxycarbonyl group having a C12 alkyl group can be mentioned.

As the aryl group in R _{1a to} R _15a of the formula (1), for example, an aromatic hydrocarbon residue such as phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, benzopyrenyl group; pyridyl group, pyrazyl group, pyrimidyl Groups, quinolyl groups, isoquinolyl groups, pyrrolyl groups, indolenyl groups, imidazolyl groups, carbazolyl groups, thienyl groups, furyl groups, and the like, and the like. These aryl groups may have a substituent, and examples thereof include an alkyl group, an alkoxy group, a halogen atom, a sulfo group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, and a cyano group.

The anion moiety in the formula (1) is C _n X _m H _{(2n + 1-m)} SO ₃ ⁻ (wherein the carbon number n is 1 to 10, the halogen atom number m is 1 ≦ m ≦ 2n + 1, a hydrogen atom The number is 2n + 1-m), and the alkyl group has at least one halogen atom X, and X is a fluorine atom or a chlorine atom. , Bromine atom and iodine atom, and fluorine atom is particularly preferable. As a perfluoroalkyl sulfonate which is an anion part, for example, nonafluorobutane sulfonate and trifluoromethane sulfonate are preferable, and trifluoromethane sulfonate is particularly preferable.

  Although the specific example represented by the said Formula (1) is shown to the following Table 1-1 and Table 1-2, this invention is not limited to these.

表１−２

Table 1-1

Table 1-2

In the colorant compound represented by the formula (2) that can be used in the colored resin composition of the present invention, examples of the C1-C30 alkyl group represented by R _{1b to} R _6b include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Group, butyl group, 1-methylpropyl group (s-butyl group), isobutyl group, pentyl group, 1-ethylpropyl group, 1-methylbutyl group, cyclopentyl group, hexyl group, 1-methylpentyl group, 1-ethylbutyl group Cyclohexyl group, hydroxypropyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, 2-heptyl group, heptyl Group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, Tradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, aralkyl group, eicosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group , Triacontyl group, isoheptyl group, isooctyl group, isononyl group, isodecyl group, isondecyl group, isododecyl group, isotridecyl group, isotetradecyl group, isopentadecyl group, isohexadecyl group, isoheptadecyl group, isooctadecyl group, isononadecyl group, Isoaraalkyl group, isoeicosyl group, isohenicosyl group, isodocosyl group, isotricosyl group, isotetracosyl group, isopentacosyl group, isohexacosyl group, isoheptacosyl group , Isooctacosyl group, isononacosyl group, isotriacontyl group, 1-methylhexyl group, 1-ethylheptyl group, 1-methylheptyl group, 1-cyclohexylethyl group, 1-heptyloctyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2,6-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,5-dimethylcyclohexane Hexyl group, 2,3-dimethylcyclohexyl group, 3,3,5-trimethylcyclohexyl group, 4-t-butylcyclohexyl group, 2-ethylhexyl group, 1-adamantyl group, 2-adamantyl group, etc. Is mentioned.

In R _{1b to} R _6b of the formula (2), the phenyl group or benzyl group may have a substituent, and examples of the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Group, (C1-C5) alkyl group such as t-butyl group and pentyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; sulfonic acid group, methoxy group, ethoxy group, propoxy group and butoxy group (C1-C6) alkoxy groups such as t-butoxy group and hexyloxy group; hydroxy (C1-C5) alkyl groups such as hydroxyethyl group and hydroxypropyl group; methoxyethyl group, ethoxyethyl group, ethoxypropyl group, butoxy (C1-C5) alkoxy (C1-C5) alkyl groups such as ethyl group; hydroxy such as 2-hydroxyethoxy group C1-C5) alkoxy group, a 2-methoxyethoxy group, 2-ethoxy alkoxy (C1-C5) alkoxy group such as ethoxy group; 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, and the like.

In R _{7b to} R _20b of the general formula (2), examples of the C1-C6 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, and a cyclo group. Examples include hexyl group, hydroxypropyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, and pentafluoroethyl group.

As R _<7b > -R < _20b > of General formula (2), a hydrogen atom, a chlorine atom, or an unsubstituted C1-C6 alkyl group is preferable.

Anion in the general formula (2) Z ^- is methide anion having a higher halogenated alkyl group C1-C10, represents a sulfonyl anion or a perfluoroalkyl sulfonate, and specific examples thereof include bis trifluoromethane Examples include a sulfonylimide anion, a tristrifluoromethanesulfonyl metide anion, a trifluoromethanesulfonate, and a nonafluorobutanesulfonate, and a tristrifluoromethanesulfonyl metide anion is particularly preferable.

カチオン部の色素骨格の置換基Ｒについて、Ｍｅはメチル基、Ｅｔはエチル基、ｎ−Ｂｕはノルマルブチル基、ｉ−Ｂｕはイソブチル基、t−Ｂｕはターシャルブチル基、ｉ−Ｐｒはイソプロピル基、ｉ−Ｐｅｎはイソペンチル基、i−Ｈｅｐはイソヘプチル基、ＣＨはシクロヘキシル基、Ｐｈはフェニル基、をそれぞれ表す。 Although the specific example of the color material compound represented by Formula (2) is shown in Table 2, this invention is not limited to these. Table 2 shows the substituted alkyl part of the cation part, and the anion part is an alkylsulfonylimide anion, alkylsulfonylmethide anion, or alkylsulfonate having a C1-C10 higher-order halogenated alkyl group.
Table 2

Regarding the substituent R of the dye skeleton in the cationic part, Me is a methyl group, Et is an ethyl group, n-Bu is a normal butyl group, i-Bu is an isobutyl group, t-Bu is a tertiary butyl group, and i-Pr is isopropyl. I-Pen represents an isopentyl group, i-Hep represents an isoheptyl group, CH represents a cyclohexyl group, and Ph represents a phenyl group.

The colorant compounds of the formulas (1) and (2) used in the colored resin composition of the present invention are described in, for example, Yutaka Hosoda “Theoretical Manufacturing Dye Chemistry” (pages 373-375) published by Gihodo Co., Ltd. It is also possible to synthesize by purchasing a commercial product in which Z ⁻ is a chlorine anion, adding a corresponding salt or acid, and exchanging the salt.

When the colorant compound in the present invention is synthesized by salt exchange, for example, the colorant compound in which Z ⁻ is a chlorine anion is reacted with a reaction solvent (for example, water, methanol, ethanol, isopropanol, acetone, N, N-dimethylformaldehyde). And water-soluble polar solvents such as amide (hereinafter abbreviated as DMF) and N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), and these solvents may be used alone or in combination. The salt or acid to be added is added in an amount of about 0.5 to 3 equivalents, stirred at a predetermined temperature (for example, 0 to 100 ° C.), and the precipitated crystals are easily obtained by filtration.

  In the colored resin composition of the present invention, the coloring material compound represented by the formula (1) indicates the total solid content (the total amount of the solid content composed of the coloring material compound, the binder resin, the curing agent, etc.). Preferably 1-60 parts by mass, more preferably 5-30 parts by mass. When the content is larger than this range, problems such as precipitation and aggregation occur, or the adhesiveness with the substrate is lowered due to insufficient curing. When the content is small, there is no big problem, but there is a possibility that sufficient color purity cannot be obtained as color characteristics.

  When the colorant compound represented by the formula (1) has low solubility in the colored resin composition, it may be used after being dispersed with a dispersant, as in the case of the optional component pigment described later. Good. Two or more colorant compounds represented by the formula (1) may be mixed or used alone, but other dyes or pigments may be mixed. Since the present invention mainly relates to blue pixels and red pixels, if necessary, it can be mixed with known blue dyes, violet dyes, red dyes and yellow dyes, or blue pigments, violet pigments, red pigments and yellow pigments. .

  The binder resin used in the present invention is desirably soluble in an alkaline developer used in a development processing step during the production of a color filter in terms of the design of a photolithography method, and further, to form a good fine pattern. Those having sufficient curing characteristics with a photopolymerization initiator, a photopolymerizable monomer and the like are desirable. The pigment-dispersed resin composition must also have good compatibility with constituent materials such as a photopolymerization initiator, a photopolymerizable monomer, and a pigment dispersion, and be stable so as not to cause precipitation or aggregation. In the case of the inkjet method, alkali solubility is not particularly required, and therefore a resin having good compatibility with other colorants and additives may be selected.

  A known resin can be used as the binder resin, but more preferably one or more of the following carboxyl groups or ethylenically unsaturated monomers having a hydroxyl group or other copolymerizable aromatic hydrocarbon groups. And a copolymer such as an ethylenically unsaturated monomer having an aliphatic hydrocarbon group. In addition, those having an epoxy group at the side chain or terminal, and epoxy acrylate resins to which acrylate is added can also be used. These monomers may be used alone or in combination of two or more.

  Specific examples of the carboxyl group-containing ethylenically unsaturated monomer that can be used in the present invention include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; Unsaturated dicarboxylic acids (anhydrides) such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; Products), 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl 2-hydroxypropyl phthalate, 2-acryloyloxyethyl 2-hydroxyethylphthalic acid, etc. These can be used alone or in admixture of two or more.

  Generally, when dispersing a pigment, a dispersant and a dispersion aid are used. There are pigment-based dispersants, resin-based dispersants, surfactants, and the like having good adsorptivity to pigments. For example, as a pigment-based dispersant, a method of mixing a sulfonated pigment or a metal salt thereof as described in Patent Document 4 with a pigment, a method of mixing a substituted aminomethyl derivative, and the like are known as known techniques. . Some resin dispersants are nonpolar nonionic, but polymer resins having an acid value, an amine value, etc. that give good pigment adsorption are common, such as acrylic resins, polyurethane resins, and polycarboxylic acids. , Polyamide resin, polyester resin and the like. Specific examples thereof include ED211 (manufactured by Enomoto Kasei), Ajisper PB821 (manufactured by Ajinomoto Fine Techno), Solsperse 71000 (manufactured by Avicia), and the like.

  Specific examples of the hydroxyl group-containing ethylenically unsaturated monomer that can be used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxy. Butyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 4-hydroxypentyl (meth) acrylate, 3-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate , 5-hydroxyhexyl (meth) acrylate, 4-hydroxyhexyl (meth) acrylate, 5-hydroxy-3-methyl-pentyl (meth) acrylate, cyclohexane-1,4-dimethanol-mono (meth) acrylate Hydroxyl groups, such as rate, 2- (2-hydroxyethyloxy) ethyl (meth) acrylate, glycerin monomethacrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) monomethacrylate The terminal polyalkylene glycol mono (meth) acrylate etc. can be mentioned, These can be used individually or in mixture of 2 or more types.

  Examples of the other copolymerizable ethylenically unsaturated monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, and m-chloro. Aromatic vinyl compounds such as styrene, p-chlorostyrene, p-methoxystyrene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl ( (Meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, paracumylphenoxyethylene glycol (meta ) Acrylate, 2-hydroxy Unsaturated carboxylic acid esters such as 3-phenoxypropyl (meth) acrylate, o-phenylphenol glycidyl ether (meth) acrylate, o-phenylphenol (meth) acrylate hydroxyethylated product, phenoxyethyl (meth) acrylate; ) Acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, norbornylmethyl (meth) acrylate, phenylnorbornyl (meth) acrylate, cyanonorbornyl (meth) acrylate, isobornyl ( (Meth) acrylate, bornyl (meth) acrylate, menthyl (meth) acrylate, fentyl (meth) acrylate, adamantyl (meth) acrylate Dimethyl adamantyl (meth) acrylate, tricyclo [5.2.1.02,6] dec-8-yl = (meth) acrylate, tricyclo [5.2.1.02,6] dec-4-methyl = (meth) acrylate, cyclodecyl (meth) ) Acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, tert-butylcyclohexyl (meth) acrylate and other alicyclic skeletons; polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly ( Hydroxyl group-terminated polyalkylene glycol mono (meth) acrylates such as ethylene glycol-propylene glycol) monomethacrylate; methoxypolyethylene glycol monomethacrylate, lauroxypolyethylene glycol mono (meth) acrylate, oct Alkyl-terminated polyalkylene glycol mono (meth) acrylates such as polyethylene glycol polypropylene glycol mono (meth) acrylate, nonylphenoxy polyethylene glycol monoacrylate, nonylphenoxy polypropylene glycol monoacrylate, allyloxy polyethylene glycol-polypropylene glycol mono (meth) acrylate Unsaturated carboxylic acid aminoalkyl esters such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate; glycidyl acrylate, Glycidyl methacrylate, 3,4-epoxybutyl (meth) acrylate Unsaturated carboxylic acid glycidyl esters such as (3,4-epoxycyclohexyl) methyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether; carboxyls such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Acid vinyl esters; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide; acrylamide , Methacrylamide, α-chloroacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, N- (meth) acryloylphthalimide, N- (2-hydroxyethyl) acryl Unsaturated amides or unsaturated imides such as amide, N- (2-hydroxyethyl) methacrylamide and maleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl acrylate and polymethyl Examples thereof include macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of a polymer molecular chain such as methacrylate, poly n-butyl acrylate, poly n-butyl methacrylate, and polysilicone. A mixture of seeds or more can be used.

  A polymer in which an unsaturated double bond is further introduced into the side chain of the copolymer is also useful. For example, an acrylate having an alcoholic hydroxyl group such as hydroxyethyl acrylate in the maleic anhydride portion of a copolymer with styrene, vinylphenol, acrylic acid, acrylic ester, acrylamide, or the like copolymerizable with maleic anhydride Acrylic acid is added to the hydroxyl group of a compound obtained by reacting an acrylate having an epoxy group, such as glycidyl methacrylate, and half-esterified, and a copolymer of acrylic acid, an acrylic ester and an acrylate having an alcoholic hydroxyl group such as hydroxyethyl acrylate. Examples thereof include reacted compounds. Moreover, urethane resin, polyamide, polyimide resin, polyester resin, commercially available ACA-200M (manufactured by Daicel), ORGA-3060 (manufactured by Osaka Organic Chemical), AX3-BNX02 (manufactured by Nippon Shokubai), UXE-3024 (Nippon Kayaku) Made), UXE-3000 (made by Nippon Kayaku), ZGA-287H (made by Nippon Kayaku), TCR-1338H (made by Nippon Kayaku), ZXR-1722H (made by Nippon Kayaku), ZFR-1401H (Nippon Kayaku) And ZCR-1642 (manufactured by Nippon Kayaku) can also be used.

  When producing the binder resin (copolymer) used in the present invention, a polymerization initiator is used. As specific examples of the polymerization initiator used when synthesizing the copolymer, α, α′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), Examples thereof include t-butyl peroctoate and di-t-butyl peroxide benzoylmethyl ethyl ketone peroxide. The usage-amount of a polymerization initiator is 0.01-25 mass parts with respect to the sum total of all the monomers used for the synthesis | combination of a copolymer. In the case of synthesizing a copolymer, it is preferable to use an organic solvent described below, but a solvent having sufficient dissolving power for the monofunctional monomer and polymerization initiator used is used. The reaction temperature when synthesizing the copolymer is preferably 50 to 120 ° C., particularly preferably 80 to 100 ° C. Moreover, it is preferable that reaction time is 1 to 60 hours, More preferably, it is 3 to 20 hours. The preferred acid value of the copolymer is 10 to 300 (mgKOH / g), and the preferred hydroxyl value is 10 to 200 (mgKOH / g). When the acid value or hydroxyl value is 10 or less, developability is lowered. As for the weight average molecular weight (Mw) of a copolymer, 2000-400000 are preferable and 3000-100000 are more preferable. When the weight average molecular weight is 2000 or less, or 400000 or more, sensitivity, developability and the like are lowered.

  In this invention, the said binder resin can be used individually or in mixture of 2 or more types. Content of binder resin in this invention is 0.5-99 mass parts normally with respect to 100 mass parts of total solids of a colored resin composition, Preferably it is 5-50 mass parts. In this case, if the content of the binder resin is less than 0.5 parts by mass, the alkali developability may be lowered, or problems such as scumming or film residue in areas other than the area where pixels are formed may occur. is there.

  Examples of the curing agent used in the present invention include a photopolymerization monomer in the case of radical polymerization, an epoxy resin in the case of ion curing, and a melamine curing agent. Specific examples of these include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol (Meth) acrylate, tetraethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, glycerol (meth) acrylate, bisphenol-A type epoxy di (meth) acrylate, bisphenol-F type epoxy Sidi (meth) acrylate, bisphenol-fluorene type epoxy di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanuric Acid tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, Kayrad RP-1040 ( Nippon Kayaku), Kayrad DPCA-30 (Nippon Kayaku), UA-33H (Shin Nakamura Chemical), UA-53H (Shin Nakamura Chemical), M-8060 (Toagosei); Thiol-based polymerization monomer TEMPIC (made by Sakai Chemical), TMMP (made by Sakai Chemical), PEMP (made by Sakai Chemical), DPMP (made by Sakai Chemical); Nippon Kayaku products NC-6000, NC-3000, EOCN as epoxy resins -1020, XD-1000, EPPN-501H, BREN-S, NC-7300L, Daicel Chemical Products 'Celoxite 2021P, EHPE3150, Cyclomer M100, Epolide PB3600, Japan Epoxy Resin Products' Epicoat 828, Epicoat YX8000, Epicoat YX4000, Silaace S510 (Chisso), TEPIC (Nissan Chemical Industry), etc .; Examples of the melamine curing agent include methylolated melamine and Mw-30 (Sanwa Chemical). These can be used alone or in admixture of two or more. These content is 1-80 mass parts with respect to 100 mass parts of total solids of a colored resin composition, Preferably it is 5-30 mass parts.

  The dye that can be used in addition to the essential components in the colored resin composition of the present invention preferably has spectral characteristics suitable for a color filter, and can be appropriately selected from dyes, organic pigments, and inorganic pigments. It can also be used alone or in combination of two or more. These content is 0-60 mass parts with respect to 100 mass parts of total solid of a colored resin composition, Preferably it is 5-30 mass parts. These various pigments and dyes are shown below.

  The organic pigment that can be used in addition to the essential components in the colored resin composition of the present invention is not particularly limited. For example, anthraquinone, phthalocyanine, triphenylmethane, benzimidazolone, quinacridone, azo chelate, azo , Isoindoline, isoindolinone, pyranthrone, indanthrone, anthrapyrimidine, dibromoanthanthrone, flavanthrone, perylene, perinone, quinophthalone, thioindigo, dioxazine, quinacridone, xanthene Examples include pigments such as pigments; lake pigments in which acid dyes, basic dyes, direct dyes and the like are insolubilized with the respective precipitating agents, and dyed lake pigments. More specifically, the color index, for example, Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76 78, 79, Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29 31, 32, 37, 39, 42, 44, 47, 49, 50, Pigment Violet 3, 4, 27, 39, Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48 : 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 8 : 5, 122, 146, 168, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, 279, Pigment Orange 43, 71, 73, Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 15 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182 185, 187, 188, 193, 194, 198, 199, 213, 214, Pigment Green 7, 36, 58, and the like. Among them, pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 75, 76, 79 and the like, which have good hue and resistance, etc .; pigments Violet 23, Pigment Red 177, 254, Pigment Yellow 83, 138, 139, 150 are preferable, and Pigment Blue 15: 6, which is a copper phthalocyanine pigment, is particularly preferable.

  The inorganic pigment that can be used in combination with the essential components in the colored resin composition of the present invention is not particularly limited, but examples thereof include composite metal oxide pigments, carbon black, black low-order titanium oxide, titanium oxide, barium sulfate, and zinc white. , Lead sulfate, yellow lead, bengara, ultramarine, bitumen, chromium oxide, antimony white, iron black, red lead, zinc sulfide, cadmium yellow, cadmium red, zinc, manganese purple, cobalt purple, barium sulfate, magnesium carbonate, etc. Examples thereof include oxides, metal sulfides, sulfates, metal hydroxides, and metal carbonates.

  The dye that can be used in addition to the essential components in the colored resin composition of the present invention is not particularly limited, and examples thereof include acid dyes, basic dyes, direct dyes, sulfur dyes, vat dyes, naphthol dyes, reactive dyes, and disperse dyes. It is done. Among them, any dye that is soluble in an organic solvent may be used, but even a dye that is insoluble in an organic solvent can be appropriately used by forming a dispersion. Dyes that are insoluble in organic solvents are well-known formulations, for example, in the case of acidic dyes, they can be modified to amine salt dyes by reacting organic amine compounds (for example, n-propylamine, ethylhexylpropionic acid amine, etc.) It is known that the organic amine compound is reacted with a sulfonic acid group to be modified into a dye having a sulfonamide group. These amine-modified dyes can also be used in the colored resin composition of the present invention. Specific examples of the dye include a color index, for example, C.I. number basic blue 7, acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51. 62, 70, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 249 256, 259, 267, 278, 280, 285, 290, 296, 315, 324, 335, 340, Basic Blue 7, 11, 15, 26, Solvent Blue 2, 3, 4, 5, 6, 23, 25 35, 37, 38, 43, 55, 59, 67, 72, 124, Basic violet 10, Acid violet 17, 49, Solvent Iolette 4, 5, 14, Basic Red 1, 10, 29, Acid Red 91, 92, 97, 114, 138, 151, 289, Solvent Red 45, 49, 127, Acid Yellow 17, 23, 25, 29, 38 40, 42, 76, Solvent Yellow 4, 14, 15, 24, 76, 81, 82, 94, 98, 162, Solvent Orange 2, 7, 11, 15, 26, 56, Acid Green 9, 16, etc. Is mentioned.

  The photopolymerization initiator used in the colored resin composition of the present invention used in the photographic method is preferably one having sufficient sensitivity to ultraviolet rays emitted from an ultra-high pressure mercury lamp generally used as an exposure light source, and radical polymerization. Curable photo radical initiators, ion curable photo acid generators or photo base generators. In photopolymerization, a component of a polymerization accelerator called a sensitizer that can be cured with less exposure energy can be used in combination. The photopolymerization initiator that can be used is not particularly limited. Specific examples include benzyl, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, benzoylbenzoic acid, and benzoylbenzoic acid. Acid esterified product, 4-benzoyl-4′-methyldiphenyl sulfide, benzyldimethyl ketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, isopropylthioxanthone, dimethylthioxanthone, diethylthioxanthone, diisopropyl Thioxanthone, dimethylaminomethylbenzoate, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, methylbenzoyl formate 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4-bis (Trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-s-triazine, 2,4- Bis (tribromomethyl) -6- (4′-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (tribromomethyl) 1,3,5-s-triazine, 2,4-bis (trichloromethyl) -6- (1,3-benzodioxolan-5-yl) -1,3,5-s-triazine, benzophenone, benzoylbenzoic acid 1- (4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-O— Acetate, 1- (4-methylsulfanylphenyl) butan-1-oneoxime-O-acetate, 4,4′-bis (diethylamino) benzophenone, P-dimethylaminobenzoic acid isoamyl ester, P-dimethylaminobenzoic acid ethyl ester, 2,2′-bis (O-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimi Dozol, diazonaphthoquinone initiator, and commercially available Kayacure DMBI, Kayacure BDK, Kayacure BP-100, Kayacure BMBI, Kayacure DETX-S, Kayacure EPA (all manufactured by Nippon Kayaku), Darocure 1173, Darocure 1116 (Iremo Merck) Japan)), Irgacure 907, Irgacure 369 (Ciba Specialty Chemicals), Irgacure 379EG (Ciba Specialty Chemicals), Irgacure OX-01 (Ciba Specialty Chemicals), Irgacure OXE- 02 (Ciba Specialty Chemicals), Irgacure PAG103 (Ciba Specialty Chemicals), TME-Triazine (Sanwa Chemical), Biimi Tetrazole (Kurogane Kasei), STR-110, STR-1 (manufactured by less Bae Chemicals any), and the like.

  In the case of a thermosetting resin composition used in an inkjet method or the like, a thermal polymerization initiator is generally used, but it may be used in combination with a photopolymerization initiator as necessary. Examples of the thermal polymerization initiator include azo compounds and organic peroxides, such as 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), Examples include 2,2′-azobis (2-methylbutyronitrile), di-t-butyl peroxide, dibenzoyl peroxide, cumylperoxyneodecanoate, and the like.

  These initiators can be used alone or in combination of two or more as required. These contents are 0.5 to 50 parts by mass, preferably 1 to 25 parts by mass when the solid content of the colored resinous composition is 100 parts by mass.

  The organic solvent used in the present invention has sufficient dissolving power with respect to the binder resin, photopolymerizable monomer, photopolymerization initiator, and the like, which are components of the colored resin composition, and is a monofunctional compound used for the synthesis of the binder resin. Those having sufficient dissolving power for monomers, polymerization initiators and the like can be used. Moreover, what can maintain dispersion stability can also be used when preparing a pigment dispersion.

  The organic solvent used in the present invention is not particularly limited as long as it can be used. Specific examples include benzenes such as benzene, toluene and xylene; cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; methyl cellosolve acetate. Cellosolve acetates such as ethyl cellosolve acetate and butyl cellosolve acetate; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate; methyl methoxypropionate, methoxypropion Propionates such as ethyl acrylate, methyl ethoxypropionate, ethyl ethoxypropionate; methyl lactate, lactic acid Lactic acid esters such as chill and butyl lactate; Diethylene glycols such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; Acetic esters such as methyl acetate, ethyl acetate and butyl acetate; Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane; Examples thereof include ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone; alcohols such as methanol, ethanol, butanol, isopropyl alcohol, and benzyl alcohol.

  You may use these individually or in combination of 2 or more types. Moreover, 40-10000 mass parts is preferable with respect to 100 mass parts of total solids of a colored resin composition, and, as for the usage-amount of an organic solvent, 100-1000 mass parts is more preferable.

  The colored resin composition of the present invention is produced by mixing and stirring the binder resin, curing agent, specific colorant compound, organic solvent, and the like with a dissolver, a homomixer, or the like. In addition, other pigments and dyes can be added as necessary, but if the pigment or dye has low solubility, a dispersion is obtained by a dispersing machine such as a paint shaker using an appropriate dispersant, In addition to the colored resin composition, it is mixed.

  The colored resin composition of the present invention may further include various additives, for example, fillers, surfactants, photopolymerization initiators, thermal polymerization initiators, polymerization inhibitors, adhesion promoters, antioxidants, as necessary. An ultraviolet absorber, an aggregation inhibitor, etc. can be added. In addition, the colored resin composition of the present invention can be microfiltered with a filter or the like in order to remove foreign matters after the preparation.

  Next, a method for preparing the cured product from the colored resin composition of the present invention will be described. First, the colored resin composition of the present invention is formed on a glass substrate, a silicon substrate or the like by a method such as spin coating, roll coating, slit and spin, die coating, or bar coating. .1 to 20 μm, more preferably 0.5 to 5 μm, if necessary, in a vacuum chamber, drying conditions, temperature 23 to 150 ° C., time 1 to 60 minutes, more preferably temperature The film is dried under reduced pressure at 60 to 120 ° C. for 1 to 10 minutes, and further pre-baked with a hot plate or a clean oven to form a film. Next, a general photolithography method is used to irradiate radiation (for example, an electron beam or ultraviolet rays, with ultraviolet rays being preferred) through a predetermined mask pattern, and a surfactant aqueous solution, an alkaline aqueous solution, or a surfactant and an alkaline agent. Develop with a mixed aqueous solution. Development methods include a dip method, a spray method, a shower method, a paddle method, and an ultrasonic development method, and any of these methods may be combined. The unirradiated part is removed by development, and after rinsing with water, the post-baking treatment is performed, for example, at a temperature of 130 to 300 ° C. for 1 to 120 minutes, more preferably at a temperature of 150 to 250 ° C. for 1 to 30 minutes. Under the condition, a pixel made of the colored cured film of the present invention is obtained.

  In the above, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, etc. can be used as the surfactant. Moreover, as an alkaline agent, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. are used. In the present invention, it is preferable to use an aqueous solution containing both an alkali agent and a surfactant. Development is usually performed at a processing temperature of 10 to 50 ° C., preferably 20 to 40 ° C., for a processing time of usually 30 to 600 seconds, preferably 30 to 120 seconds.

  The cured product of the colored resin composition of the present invention is useful as a color filter suitable for a liquid crystal display device, an organic EL display, a solid-state image sensor used in a digital camera, etc., and the color filter is as described above. It has the patterned pixel which consists of hardened | cured material of the colored resin composition of this invention prepared in this way.

  The liquid crystal display device of the present invention is produced, for example, with a structure in which a backlight, a polarizing film, a display electrode, a liquid crystal, an alignment film, a common electrode, a color filter of the present invention, a polarizing film, and the like are laminated in this order. The organic EL display is manufactured by forming a color filter on either the upper or lower side of the multilayer organic light emitting element. The solid-state imaging device is manufactured, for example, by providing the color filter layer of the present invention on a silicon wafer provided with transfer electrodes and photodiodes, and then laminating microlenses.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, “part” means “part by mass” unless otherwise specified. Further, the spectral transmittance was measured with a spectrophotometer “Shimadzu UV-3150”, the chromaticity in the XYZ color system was calculated, and the resistance of the colored body was evaluated.

Synthesis example 1
In a 2000 ml beaker, 4 parts of rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.) of the following formula (100) and 750 parts of water were charged and stirred at room temperature for 30 minutes. A solution prepared by dissolving 1.5 parts of a lithium salt of trifluoromethylsulfonic acid in 10 parts of water was added dropwise thereto and stirred for 3 hours. The precipitated dye was collected by filtration, washed with water and dried to obtain 3.5 parts of the dye (Compound 1). Maximum absorption wavelength: 560 nm (cyclohexanone)

Synthesis example 2
Dissolve in 50 parts of Basic Blue 7 (manufactured by Tokyo Chemical Industry Co., Ltd., decomposition temperature: 217 ° C.) of the following formula (101) and dissolve 2.1 parts of cesium salt of tristrifluoromethanesulfonium metide in 30 parts of acetonitrile while stirring. The solution was added. After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to obtain 1.5 parts of blue crystals (Compound 2).
Maximum absorption wavelength 610nm (cyclohexanone)

Synthesis Example 3 (Preparation of binder resin (copolymer))
A 500 ml four-necked flask is charged with 160 parts of methyl ethyl ketone, 10 parts of methacrylic acid, 33 parts of benzyl methacrylate, and 1 part of α, α'-azobis (isobutyronitrile), and nitrogen gas is introduced into the flask for 30 minutes while stirring. did. Then, it heated up to 80 degreeC and stirred for 4 hours as it was at 80-85 degreeC. After completion of the reaction, the reaction mixture was cooled to room temperature to obtain a colorless, transparent and uniform copolymer solution. This was precipitated in a 1: 1 mixed solution of isopropyl alcohol and water, filtered, and the solid content was taken out and dried to obtain a copolymer (A). The resulting copolymer (A) had a polystyrene equivalent weight average molecular weight of 18,000 and an acid value of 152.

Example 1
5.7 parts of copolymer (A) as binder resin, 6 parts of Kayrad DPHA (manufactured by Nippon Kayaku) as photopolymerizable monomer, 2.4 parts of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as photopolymerization initiator Then, 0.6 part of Compound 1 of Synthesis Example 1 as a dye, 17 parts of cyclopentanone and 13.3 parts of propylene glycol monomethyl ether acetate as a solvent are mixed to obtain a violet colored resin composition of the present invention. It was.

Example 2
5.7 parts of copolymer (A) as binder resin, 6 parts of Kayrad DPHA (manufactured by Nippon Kayaku) as photopolymerizable monomer, 2.4 parts of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as photopolymerization initiator , 0.3 part of Compound 1 of Synthesis Example 1 as a dye, 0.3 part of Compound 2 of Synthesis Example 2, 17 parts of cyclopentanone and 13.3 parts of propylene glycol monomethyl ether acetate as a solvent, A blue colored resin composition of the present invention was obtained.

Example 3
C. I. Pigment Blue 15: 6 / Addisper PB821 / Solsperse 5000 / PGMEA = 15.0 / 6.0 / 1.0 / 78.0 (mass ratio) After mixing, 400 parts of 0.3 mm zirconia beads were added. Then, a blue pigment dispersion 1 was obtained by performing a treatment for 60 minutes with a paint shaker and filtering. 24 parts of Blue Dispersion 1 was added to the colored resin composition obtained in Example 1 to obtain the blue colored resin composition of the present invention.

Example 4
24 parts of Blue Dispersion 1 was added to the colored resin composition obtained in Example 2 to obtain the blue colored resin composition of the present invention.

Comparative Example 1
A violet colored resin composition was obtained with the same composition as in Example 1 except that Compound 1 of Synthesis Example 1 was changed to Rhodamine B.

Comparative Example 2
A blue colored resin composition was obtained with the same composition as in Example 1 except that Compound 1 in Synthesis Example 1 was changed to Basic Blue 7.

Comparative Example 3
A blue resin composition was obtained with the same composition as in Example 1 except that Compound 1 of Synthesis Example 1 was changed to 50 parts of the blue resin composition of Example 3.

Patterning Evaluation The colored resin composition (Examples 1 to 4) obtained above was applied on the substrate, pre-baked under conditions of 80 ° C. × 100 seconds, then cured by exposure through a mask, and then a surfactant. After developing with an aqueous alkaline solution containing, rinsing with water, heating at 200 ° C. gave a colored pattern. The obtained colored pattern had a resolution of 5 μm square in a line and space, and no residue or peeling of pixels was confirmed.

Regarding Evaluation of Heat Resistance and Contrast A substrate for heat resistance and light resistance evaluation was prepared by applying each composition to a glass substrate in the same manner as described above, exposing the entire surface, and treating the substrate at 200 ° C. for 5 minutes. . Thereafter, each evaluation was performed as described below. The heat resistance was evaluated by measuring the transmittance of the evaluation substrate with a spectrophotometer, then treating it at 200 ° C. for 120 minutes, measuring the spectral transmittance again, and calculating the color difference (ΔEab). Contrast was measured with a contrast meter (CT-1 manufactured by Osaka Co., Ltd.) using the evaluation substrate, and the luminance value (cd / cm ² ) when the ^two polarizing plates were parallel to each other (cd / cm ² ). The contrast was calculated from the ratio of cm ² ) (brightness value in parallel / brightness value in orthogonal).
Table 3 shows the results of heat resistance, and Table 4 shows the results of contrast.

比較例１では耐熱処理前の硬化ベーク（２００℃下で５分間）中に色素の消色が認められ、耐熱性が著しく劣る結果となった。 Table 3 Evaluation results of heat resistance

In Comparative Example 1, decoloring of the dye was observed during the curing bake before heat-resistant treatment (5 minutes at 200 ° C.), resulting in extremely poor heat resistance.

表３の結果から、本発明の実施例１〜４は比較例１及び２の従来型の染料と比較して耐熱性が向上していることが分かった。実施例３及び４については顔料を併用したものであるが、青色や赤色等の様々な色特性を有する本発明の色材化合物と顔料を混合しても特に析出することなく良好な結果を示している。表４の結果より本発明の実施例４は化合物１（キサンテン類）と化合物２（トリアリールメタン類）との組み合わせたものであるが顔料を含む比較例３と比べてコントラストが大きく向上していることが分かった。本発明の色材化合物は他の染料を混合しても特に析出することなく良好な結果を示した。 Table 4 Contrast evaluation results

From the results in Table 3, it was found that Examples 1 to 4 of the present invention had improved heat resistance as compared with the conventional dyes of Comparative Examples 1 and 2. In Examples 3 and 4, pigments were used in combination, but even when the colorant compound of the present invention having various color characteristics such as blue and red and the pigment were mixed, good results were obtained without any particular precipitation. ing. From the results of Table 4, Example 4 of the present invention is a combination of Compound 1 (xanthenes) and Compound 2 (triarylmethanes), but the contrast is greatly improved as compared with Comparative Example 3 containing a pigment. I found out. The colorant compound of the present invention showed good results without any precipitation even when other dyes were mixed.

  As described above, the colored resin composition of the present invention using a specific colorant compound is clear, has excellent color filter characteristics (heat resistance, contrast, etc.), and has a high quality and high reliability. Pixels can be obtained. In addition, it can be used by being well mixed with pigments and other dyes depending on the application, and shows wide applicability, so it can be said that the industrial value is high.

Claims (9)

Colored resin composition for color filters containing a colorant compound represented by the following formula (1), a binder resin, a solvent, and a curing agent

(In Formula (1), R < _1a > -R < _6a > respectively independently represents a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a nitro group, a carboxyl group, and an alkoxycarbonyl group. _7a to R _10a each independently represent a hydrogen atom, an alkyl group of C1-C12, an aryl group _{.R 11a} to R _15a each independently represent a hydrogen atom, C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen It may have one or more of atoms, nitro group, phenoxy group, carboxyl group, alkoxycarbonyl group, sulfo group, sulfamoyl group, and the anion part is a C1-C10 higher order halogenated alkyl sulfonate. , Having at least one halogen atom (n = 1 to 10, 1 ≦ m ≦ 2n + 1, X is a halogen atom Any). The coloring resin composition of Claim 1 containing the coloring material compound represented by Formula (1) which uses trifluoromethanesulfonate as an anion part. The colored resin composition according to claim 1 or 2, comprising a metal phthalocyanine pigment. The coloring resin composition as described in any one of Claims 1 thru | or 3 containing the coloring material compound represented by following formula (2).

(In Formula (2), R _{1b to} R _6b each independently represents a hydrogen atom, a C1-C30 alkyl group, a phenyl group, or a benzyl group, but at least one is a C1-C30 alkyl group. R _7b to R _20b each independently represent a hydrogen atom, a halogen atom, .Z represents an alkyl group of C1-C6 ^- alkylsulfonyl imide anion having a higher halogenated alkyl group C1-C10, alkylsulfonyl methide anion, or Represents alkyl sulfonate). 5. The colorant compound represented by the formula (2), wherein the anion part Z ⁻ of the formula (2) is a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion or a trifluoromethanesulfonate, The colored resin composition according to claim 1. A colored cured film for a color filter, which is patterned using the colored resin composition according to any one of claims 1 to 5. A color filter comprising the colored cured film for a color filter according to claim 6. A liquid crystal display device and an organic EL display comprising the color filter according to claim 7. A solid-state imaging device comprising the color filter according to claim 8.